WO2022113627A1 - Batterie de stockage au plomb-acide - Google Patents

Batterie de stockage au plomb-acide Download PDF

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WO2022113627A1
WO2022113627A1 PCT/JP2021/039747 JP2021039747W WO2022113627A1 WO 2022113627 A1 WO2022113627 A1 WO 2022113627A1 JP 2021039747 W JP2021039747 W JP 2021039747W WO 2022113627 A1 WO2022113627 A1 WO 2022113627A1
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Prior art keywords
negative electrode
electrode plate
lead
less
group
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PCT/JP2021/039747
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English (en)
Japanese (ja)
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力郎 小嶋
宏樹 籠橋
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株式会社Ｇｓユアサ
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Priority to JP2022565148A priority Critical patent/JPWO2022113627A1/ja
Publication of WO2022113627A1 publication Critical patent/WO2022113627A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • H01M50/541—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor

Definitions

  • the present invention relates to a lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use, industrial use, and so on.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Each electrode plate comprises a current collector and an electrode material.
  • An ear portion for connecting to an external terminal is provided on the upper part of the current collector.
  • Lead-acid batteries may be used in an undercharged state called a partially charged state (PSOC).
  • PSOC partially charged state
  • ISS idling stop start
  • the lead-acid battery is repeatedly charged and discharged by PSOC, the thickness of the ear portion of the negative electrode plate is reduced due to corrosion, resulting in ear thinning, which may reduce the life performance. From the viewpoint of suppressing such corrosion of the selvage, it is being studied to provide a surface layer on the selvage.
  • Patent Document 1 is a lead storage battery including a positive electrode plate, a negative electrode plate, and an electrolytic solution.
  • a negative current collector having an ear portion for collecting electricity is provided so as to project from the edge portion, and a Pb—Sn-based alloy or a Pb-Sb-based alloy is provided on the surface of at least one of the edge portion and the ear portion.
  • a surface layer containing an alloy, a Pb-Sn-Sb-based alloy, and an alloy or metal selected from Sn is formed, and the electrolytic solution contains sodium ion, potassium ion, magnesium ion, aluminum ion, phosphoric acid and boric acid.
  • additives may be added to the constituent members of lead-acid batteries from the viewpoint of imparting various functions.
  • Patent Document 2 proposes a lead-acid battery in which a copolymer of propylene oxide and ethylene oxide is added to a negative electrode plate active material in combination with lignin sulfonic acid.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage has a surface layer containing Sn and The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material relates to a lead storage battery containing a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage has a surface layer containing Sn and The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material relates to a lead storage battery containing a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit.
  • the Sn oxidation reaction and reduction reaction are unlikely to occur. Therefore, if a surface layer containing Sn is provided on the ear portion of the negative electrode plate, the oxidation reaction and reduction reaction involving lead in the ear portion are less likely to occur due to the shielding effect of Sn. As a result, when the surface layer containing Sn is provided on the selvage portion of the negative electrode plate, the ear thinning in the PSOC cycle is reduced as compared with the case where the surface layer is not provided. Therefore, as the Sn content in the surface layer increases, ear thinning is reduced.
  • the Sn content is large, in addition to being disadvantageous in terms of cost, the amount of gas generated during overcharging is large, so that the amount of decrease in the electrolytic solution is large. From the viewpoint of cost reduction and reduction of the amount of decrease in the electrolytic solution during overcharging, it is advantageous to keep the Sn content of the surface layer low.
  • the Sn content is less than 10% by mass, it has been considered difficult to suppress ear thinning in the PSOC cycle by the surface layer containing Sn.
  • the lead-acid battery includes at least one cell including a group of plates and an electrolytic solution.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage portion comprises a surface layer containing Sn. The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material contains a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent. In the above 1 H-NMR spectrum, the peak appearing in the chemical shift range of 3.2 ppm or more and 3.8 ppm or less is derived from the oxyC 2-4 alkylene unit.
  • the lead-acid battery according to another aspect of the present invention includes at least one cell including a group of plates and an electrolytic solution.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage portion comprises a surface layer containing Sn. The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material contains a polymer compound containing a repeating structure of oxyC 2-4 alkylene units.
  • the negative electrode material contains the polymer compound as described above.
  • a negative electrode current collector having a surface layer containing Sn in the selvage
  • ear thinning in the PSOC cycle is reduced even when the Sn content in the surface layer is less than 10% by mass. can.
  • the negative electrode material contains a polymer compound, which suppresses gas generation during overcharging, resulting in a decrease in the electrolytic solution (hereinafter, simply reduced solution). It may be called.) Can be reduced.
  • the reason why the ear thinning in the negative electrode plate in the PSOC cycle is reduced by containing the above polymer compound in the negative electrode electrode material is as follows. First, when the negative electrode electrode material contains the above polymer compound, the polymer compound is present in the vicinity of lead, which is the negative electrode active material. As a result, in the PSOC cycle, the potential of the negative electrode plate shifts in a low direction. Since the potential of the selvage portion of the negative electrode plate also shifts in a low-key direction, the reduction reaction from lead sulfate to lead during charging tends to proceed. In addition to the effect of shielding Sn in the ears, lead sulfate is less likely to accumulate, so that it is possible to reduce ear thinning even though the Sn content in the surface layer is as low as less than 10% by mass.
  • the low Sn content in the surface layer suppresses the gas generation reaction involving Sn during overcharging.
  • the potential of the negative electrode plate shifts in a low direction, the hydrogen overvoltage becomes large, so that the generation of hydrogen gas in the negative electrode plate during overcharging is suppressed. In this way, gas generation is suppressed during overcharging, so that liquid reduction can be reduced.
  • the effect of suppressing ear thinning in the negative electrode plate in the PSOC cycle and the effect of suppressing liquid loss during overcharging can be obtained even when the content of the polymer compound in the negative electrode material is very small (for example, less than 0.01% by mass). Be done. From this, it is considered that the action of the oxyC 2-4 alkylene unit of the polymer compound contained in the negative electrode electrode material exerts a high adsorption action on lead. Further, it is considered that the potential of the entire negative electrode plate including the selvage is likely to shift in a low-key direction when the polymer compound is thinly spread on the surface of lead.
  • the polymer compound spreads thinly on the surface of lead, so that the hydrogen overvoltage rises in a wide range of the lead surface of the negative electrode plate, and the side reaction that hydrogen is generated by the reduction of protons during overcharging is inhibited. It is thought that it will be done.
  • the fact that the polymer compound is thinly spread on the surface of lead is consistent with the fact that the polymer compound tends to have a linear structure. Therefore, it is important that the polymer compound is contained in the negative electrode material regardless of whether or not it is contained in the components of the lead storage battery other than the negative electrode material.
  • the polymer compound may contain an oxygen atom bonded to a terminal group and an -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom.
  • the integrated value of the peak of 3.2 ppm to 3.8 ppm, the integrated value of the peak of the hydrogen atom of -CH 2 -group bonded to the oxygen atom, and the -CH ⁇ group bonded to the oxygen atom is preferably 85% or more.
  • Such polymer compounds contain a large amount of oxyC 2-4 alkylene unit in the molecule. Therefore, it is considered that the polymer compound is easily adsorbed on lead and easily has a linear structure, so that the lead surface can be easily covered thinly. Therefore, the effect of reducing the ear thinning of the negative electrode plate in the PSOC cycle can be further enhanced, and the effect of suppressing the liquid reduction at the time of overcharging can be further improved.
  • the polymer compound having a peak in the chemical shift range of 3.2 ppm to 3.8 ppm preferably contains a repeating structure of an oxyC 2-4 alkylene unit.
  • a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit it is considered that the polymer compound is more easily adsorbed to lead and easily has a linear structure, so that the lead surface can be easily covered thinly. .. Therefore, it is advantageous in further enhancing the effect of suppressing the ear thinning of the negative electrode plate in the PSOC cycle and the liquid reduction at the time of overcharging.
  • the polymer compound may contain at least one selected from the group consisting of hydroxy compounds having a repeating structure of oxyC 2-4 alkylene units, etherified compounds of hydroxy compounds and esterified compounds of hydroxy compounds.
  • the hydroxy compound is selected from at least a group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a poly C 2-4 alkylene oxide adduct of a polyol. It is a kind. When such a polymer compound is used, it is possible to further suppress the ear thinning of the negative electrode plate in the PSOC cycle and the liquid loss at the time of overcharging.
  • the repeating structure of the oxyC 2-4 alkylene unit may include at least the repeating structure of the oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ). It is considered that such a polymer compound has a high adsorptivity to lead, but easily spreads thinly on the lead surface, and has an excellent balance between them. Therefore, the liquid reduction can be reduced more effectively. In addition, the thinning of the ears of the negative electrode plate can be further reduced.
  • the polymer compound has a high adsorptivity to lead and can cover the lead surface thinly, so that the content of the polymer compound in the negative electrode electrode material is very small (more specifically, 400 ppm or less). ), It is possible to reduce the thinning of the ears of the negative electrode plate in the PSOC cycle and the reduction of liquid during overcharging. From the viewpoint of ensuring a higher ear thinning suppressing effect and liquid thinning suppressing effect, the content of the polymer compound in the negative electrode electrode material is preferably 15 ppm or more.
  • the polymer compound can be contained in the negative electrode material, and the origin of the polymer compound contained in the negative electrode material is not particularly limited.
  • the polymer compound may be contained in any of the components of the lead-acid battery (for example, the negative electrode plate, the positive electrode plate, the electrolytic solution, and the separator) when the lead-acid battery is manufactured.
  • the polymer compound may be contained in one component or in two or more components (for example, a negative electrode plate and an electrolytic solution).
  • the Sn content in the surface layer of the selvage is preferably 7% by mass or less. Even when the Sn content is so low, the action of the polymer compound can reduce ear thinning and reduce liquid loss.
  • the Sn content in the surface layer of the selvage is preferably 0.01% by mass or more. In this case, the effect of suppressing ear thinning due to Sn can be obtained. Further, even when the Sn content is such a small amount, a high effect can be ensured in reducing ear thinning and liquid reduction due to the action of the polymer compound.
  • the electrode plate group includes a plurality of positive electrode plates and a plurality of negative electrode plates, and has a structure in which the positive electrode plates and the negative electrode plates are alternately laminated via a separator. , It is preferable to provide 9 or more negative electrode plates.
  • the number of plates included in the plate group increases, the decrease in the specific gravity of the electrolytic solution in the upper part of the plate group is suppressed. As a result, the dissolution of lead is suppressed, so that the effect of suppressing ear thinning of the negative electrode plate is further enhanced.
  • the relationship between the distance between the positive electrode plate and the negative electrode plate (distance between the electrodes D) and the maximum thickness T of the separator in the electrode plate group is DT ⁇ 0.15 mm or less.
  • the relationship between the electrode distance D and the separator maximum thickness T is in such a range, the effect of suppressing a decrease in the specific gravity of the electrolytic solution in the upper part of the electrode plate group is further enhanced. Since the decrease in the specific gravity of the electrolytic solution around the ear is further suppressed, the effect of suppressing the ear thinning of the negative electrode plate is further enhanced.
  • the electrolytic solution preferably contains Al ions.
  • the effect of suppressing the decrease in the specific gravity of the electrolytic solution around the selvage is further enhanced, so that the effect of suppressing the ear thinning of the negative electrode plate is further enhanced.
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery (VRLA type lead-acid battery) or a liquid type (vent type) lead-acid battery.
  • the Sn content in the surface layer of the ear portion of the negative electrode plate, the content of the polymer compound in the negative electrode electrode material, the electrode distance D, and the maximum thickness T of the separator are taken out from the fully charged lead-acid battery. It is required for the negative electrode plate, the electrode plate group, or the separator.
  • the vertical direction of the lead-acid battery or the component of the lead-acid battery means the vertical direction of the lead-acid battery in the state where the lead-acid battery is used.
  • Each electrode plate of the positive electrode plate and the negative electrode plate is provided with an ear portion for connecting to an external terminal.
  • the ears are provided so as to project laterally to the sides of the plate, but in many lead-acid batteries, the ears are usually made of the plate. It is provided so as to project upward at the top.
  • the outer layered portion having different properties (color, state of metal particles, etc.) from the inner layer is defined as the surface layer.
  • the negative electrode material is usually held in the current collector.
  • the negative electrode material is a portion obtained by removing the current collector from the negative electrode plate.
  • Members such as mats and pacing papers may be attached to the negative electrode plate. Since such a member (also referred to as a sticking member) is used integrally with the negative electrode plate, it is included in the negative electrode plate.
  • the negative electrode plate includes a sticking member (mat, pacing paper, etc.)
  • the negative electrode electrode material is a portion of the negative electrode plate excluding the current collector and the sticking member.
  • the polymer compound satisfies at least one of the following conditions (i) and (ii).
  • Condition (i) The polymer compound has a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • Condition (ii) The polymer compound comprises a repeating structure of oxyC 2-4 alkylene units.
  • condition (i) the peak in the range of 3.2 ppm or more and 3.8 ppm or less is derived from the oxyC 2-4 alkylene unit. That is, the polymer compound satisfying the condition (ii) is also a polymer compound satisfying the condition (i).
  • the polymer compound satisfying the condition (i) may contain a repeating structure of a monomer unit other than the oxyC 2-4 alkylene unit, and may have a certain molecular weight.
  • the number average molecular weight (Mn) of the polymer compound satisfying the above (i) or (ii) may be, for example, 300 or more.
  • the oxy C 2-4 alkylene unit is a unit represented by —OR 1 ⁇ (where R 1 indicates a C 2-4 alkylene group).
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the distance between the poles D is expressed by the following equation.
  • Distance between poles D (pitch-thickness of positive electrode plate-thickness of negative electrode plate) / 2
  • the pitch is an average value of the distances between the centers of the selvages of the pair of adjacent positive electrode plates. More specifically, the pitch is the average value of the center-to-center distances of the selvages obtained for all adjacent positive electrode plate pairs included in the electrode plate group.
  • the pitch is the average value of one electrode plate group (cell) located at the end and one electrode plate group (cell) located near the center.
  • the thickness of the positive electrode plate is the average value of the thicknesses of all the positive electrode plates included in the electrode plate group
  • the thickness of the negative electrode plate is the average value of the thicknesses of all the negative electrode plates included in the electrode plate group.
  • the maximum thickness T of the separator is an average value of the maximum thickness t of all the separators included in the electrode plate group (cell).
  • the maximum thickness T of the separator is one plate group (cell) located at the end and one plate group (cell) located near the center. ) Is the average value.
  • the thickness of the separator is a thickness including the base portion and the ribs.
  • the thickness of the separator is the thickness of the base portion, the height of the rib on one main surface from the base portion, and the thickness of the rib on the other main surface from the base portion. It is the total with the height.
  • the thickness of the separator in the portion where the total value is the largest is the maximum thickness t.
  • the fully charged state of a liquid lead-acid battery is defined by the definition of JIS D 5301: 2019. More specifically, the terminal voltage (V) during charging of the lead-acid battery is measured every 15 minutes with a current (A) 0.2 times the value (value whose unit is Ah) described as the rated capacity. Alternatively, the state in which the lead-acid battery is charged is regarded as a fully charged state until the electrolyte density converted to temperature at 20 ° C. shows a constant value with three valid digits three times in a row.
  • the fully charged state is a current (A) 0.2 times the value (value with the unit being Ah) described in the rated capacity in an air tank at 25 ° C. 2.23V / cell constant current constant voltage charging was performed, and the charging current during constant voltage charging became 0.005 times the value (A) described in the rated capacity (value with Ah as the unit). At that point, charging has been completed.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • An initial use battery is a battery that has not been used for a long time and has hardly deteriorated.
  • the negative electrode plate includes a current collector having an ear portion (negative electrode current collector) and a negative electrode electrode material.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of Pb-Ca-based alloy, Pb-Ca-Sn-based alloy, and Pb-Sn-based alloy. These leads or lead alloys may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like.
  • the negative electrode current collector has a surface layer at least in the selvage.
  • the surface layer of the selvage contains Sn.
  • the surface layer contains, for example, a lead alloy containing Sn. Such a surface layer can suppress ear thinning in the PSOC cycle.
  • the Sn content in the surface layer of the selvage portion is less than 10% by mass, may be 7% by mass or less, and may be 6% by mass or less or 5% by mass or less.
  • the Sn content in the surface layer is, for example, 0.01% by mass or more, may be 0.05% by mass or more, or may be 0.1% by mass or more. Even if the Sn content in the surface layer is so low, ear thinning can be reduced by combining with a negative electrode material containing a polymer compound. Further, since the Sn content is low, the effect of reducing the liquid reduction can be obtained.
  • the Sn content in the surface layer of the ear is 0.01% by mass or more and less than 10% by mass (or 7% by mass or less), 0.05% by mass or more and less than 10% by mass (or 7% by mass or less), 0. 1% by mass or more and less than 10% by mass (or 7% by mass or less), 0.01% by mass or more and 6% by mass or less (or 5% by mass or less), 0.05% by mass or more and 6% by mass or less (or 5% by mass or less) ), Or 0.1% by mass or more and 6% by mass or less (or 5% by mass or less).
  • the thickness of the surface layer of the selvage portion is, for example, 0.01 mm or more, and may be 0.015 mm or more or 0.02 mm or more.
  • the thickness of the surface layer is, for example, 0.1 mm or less, and may be 0.05 mm or less.
  • the thickness of the surface layer of the ear is 0.01 mm or more and 0.1 mm or less (or 0.05 mm or less), 0.015 mm or more and 0.1 mm or less (or 0.05 mm or less), or 0.02 mm or more and 0.1 mm or less. (Or 0.05 mm or less) may be used.
  • the selvage portion of the negative electrode plate is cut along the thickness direction, and the cut surface is observed with a metallurgical microscope. Then, the outer layered portion having different properties from the inner one is used as the surface layer, and a part thereof is scraped off to obtain a sample and the mass is measured.
  • a metallurgical microscope GX53F manufactured by OLYMPUS is used.
  • the Sn content in the surface layer is analyzed according to the lead separation inductively coupled plasma emission spectroscopy described in JIS H2105: 1955. More specifically, an aqueous solution is obtained by mixing the sample collected above with tartaric acid and dilute nitric acid. Hydrochloric acid is added to the aqueous solution to precipitate lead chloride, which is filtered and the filtrate is collected. The Sn concentration in the filtrate is analyzed by a calibration curve method using an ICP emission spectroscopic analyzer, and the Sn content in the surface layer of the ear can be determined from the Sn concentration and the mass of the collected sample. As the ICP emission spectroscopic analyzer, ICPS-8000 manufactured by Shimadzu Corporation is used.
  • the selvage portion of the negative electrode plate is impregnated with epoxy resin and cured.
  • the selvage is then cut along the thickness direction of the selvage and the cut surface is polished.
  • the thickness of the surface layer can be obtained by observing the polished cut surface with a metallurgical microscope, measuring the thickness at any five points using the outer layered portion having different properties from the inner layer as the surface layer, and averaging the thickness. ..
  • As the metallurgical microscope As the metallurgical microscope, GX53F manufactured by OLYMPUS is used.
  • the negative electrode material contains the above polymer compound.
  • the negative electrode material further contains a negative electrode active material (specifically, lead or lead sulfate) that develops a capacity by a redox reaction.
  • the negative electrode material may contain at least one selected from the group consisting of organic shrink proofing agents, carbonaceous materials, and other additives. Examples of the additive include, but are not limited to, barium sulfate, fibers (resin fibers, etc.) and the like.
  • the negative electrode active material in the charged state is spongy lead, but the unchemical negative electrode plate is usually produced by using lead powder.
  • the polymer compound has a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum.
  • Such polymer compounds have an oxyC 2-4 alkylene unit.
  • the oxyC 2-4 alkylene unit includes an oxyethylene unit, an oxypropylene unit, an oxytrimethylene unit, an oxy2-methyl-1,3-propylene unit, an oxy1,4-butylene unit, and an oxy1,3-butylene unit. And so on.
  • the polymer compound may have one kind of such oxyC 2-4 alkylene unit, or may have two or more kinds.
  • the polymer compound preferably contains a repeating structure of oxyC 2-4 alkylene units.
  • the repeating structure may contain one type of Oxy-C 2-4 alkylene unit or two or more types of Oxy-C 2-4 alkylene unit.
  • the polymer compound may contain one kind of the above-mentioned repeating structure, or may contain two or more kinds of the above-mentioned repeating structures.
  • Polymer compounds having a repeating structure of oxyC 2-4 alkylene units also include polymer compounds classified as surfactants (more specifically, nonionic surfactants).
  • polymer compound examples include a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit (poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a polyol poly C 2 ). -4 alkylene oxide adducts, etc.), ethers or esters of these hydroxy compounds, and the like.
  • copolymer examples include a copolymer containing different oxyC 2-4 alkylene units.
  • the copolymer may be a block copolymer.
  • the polyol may be any of an aliphatic polyol, an alicyclic polyol, an aromatic polyol, a heterocyclic polyol and the like. From the viewpoint that the polymer compound is thin and easily spreads on the lead surface, an aliphatic polyol, an alicyclic polyol (for example, polyhydroxycyclohexane, polyhydroxynorbornane) and the like are preferable, and an aliphatic polyol is particularly preferable.
  • the aliphatic polyol include an aliphatic diol and a polyol having more than triol (for example, glycerin, trimethylolpropane, pentaerythritol, sugar or sugar alcohol).
  • Examples of the aliphatic diol include alkylene glycols having 5 or more carbon atoms.
  • the alkylene glycol may be, for example, C 5-14 alkylene glycol or C 5-10 alkylene glycol.
  • Examples of the sugar or sugar alcohol include sucrose, erythritol, xylitol, mannitol, and sorbitol.
  • the sugar or sugar alcohol may have either a chain structure or a cyclic structure.
  • the alkylene oxide corresponds to the oxyC 2-4 alkylene unit of the polymer compound and comprises at least C 2-4 alkylene oxide. From the viewpoint that the polymer compound can easily form a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of a -OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the above oxyC 2-4 alkylene unit.
  • the —OH group has two etherified —OR groups (in the formula, R 2 is an organic group).
  • R 2 is an organic group.
  • ends of the polymer compound some ends may be etherified, or all ends may be etherified.
  • one end of the main chain of the linear polymer compound may be an ⁇ OH group and the other end may be an ⁇ OR2 group.
  • the esterified product is composed of an OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom of the terminal group) at least a part of the hydroxy compound having a repeating structure of the oxyC 2-4 alkylene unit.
  • R 3 is an organic group.
  • some ends may be esterified or all ends may be esterified.
  • the organic groups R 2 and R 3 include hydrocarbon groups.
  • the hydrocarbon group may be a hydrocarbon group having a substituent (eg, a hydroxy group, an alkoxy group, and / or a carboxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, etc.) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 30, 1 to 20 or 1 to 10, and may be 1 to 6 or 1 to 4. .
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 24 or less carbon atoms (for example, 6 to 24). The number of carbon atoms of the aromatic hydrocarbon group may be 20 or less (for example, 6 to 20), 14 or less (for example, 6 to 14) or 12 or less (for example, 6 to 12).
  • Examples of the aromatic hydrocarbon group include an aryl group and a bisaryl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the bisaryl group include a monovalent group corresponding to bisarene. Examples of the bisarene include biphenyl and bisaryl alkane (for example, bis C 6-10 aryl C 1-4 alkane (2,2-bisphenylpropane, etc.)).
  • Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 16 or less carbon atoms.
  • the alicyclic hydrocarbon group may be a crosslinked cyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may have 10 or less or 8 or less carbon atoms.
  • the alicyclic hydrocarbon group has, for example, 5 or more carbon atoms, and may be 6 or more carbon atoms.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.) and a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.).
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • Aliphatic hydrocarbon groups may be saturated or unsaturated. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a dienyl group having two carbon-carbon double bonds, and a trienyl group having three carbon-carbon double bonds.
  • the aliphatic hydrocarbon group may be linear or branched.
  • the aliphatic hydrocarbon group may have, for example, 30 or less, 26 or less or 22 or less, 20 or less or 16 or less, 14 or less or 10 or less. It may be 8 or less or 6 or less.
  • the lower limit of the number of carbon atoms is 1 or more for an alkyl group, 2 or more for an alkenyl group and an alkynyl group, 3 or more for a dienyl group, and 4 or more for a trienyl group, depending on the type of the aliphatic hydrocarbon group.
  • Alkyl groups and alkenyl groups are particularly preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • alkyl group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, i-pentyl, and s-pentyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, cis-9-heptadecene-1-yl, palmitrail and oleyl.
  • the alkenyl group may be, for example, a C 2-30 alkenyl group or a C 2-26 alkenyl group, a C 2-22 alkenyl group or a C 2-20 alkenyl group, and a C 10-20 alkenyl group. May be.
  • the polymer compounds at least one selected from the group consisting of an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • an etherified product of a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit and an esterified product of a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit.
  • it is preferable because the effect of reducing the ear thinning of the negative electrode plate can be further enhanced. Further, even when these polymer compounds are used, a high liquid reduction suppressing effect can be ensured.
  • a polymer compound having a repeating structure of an oxypropylene unit, a polymer compound having a repeating structure of an oxyethylene unit, and the like are preferable.
  • the polymer compound may have one or more hydrophobic groups.
  • the hydrophobic group include aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and long-chain aliphatic hydrocarbon groups among the above-mentioned hydrocarbon groups.
  • the long-chain aliphatic hydrocarbon group include aliphatic hydrocarbon groups having 8 or more carbon atoms among the above-mentioned aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, etc.).
  • the aliphatic hydrocarbon group preferably has 12 or more carbon atoms, and more preferably 16 or more carbon atoms.
  • a polymer compound having a long-chain aliphatic hydrocarbon group is preferable because it is unlikely to cause excessive adsorption to lead and can further reduce ear thinning.
  • the polymer compound may be a polymer compound in which at least one of the hydrophobic groups is a long-chain aliphatic hydrocarbon group.
  • the carbon number of the long-chain aliphatic hydrocarbon group may be 30 or less, 26 or less, or 22 or less.
  • the number of carbon atoms of a long-chain aliphatic hydrocarbon group is 8 or more (or 12 or more) 30 or less, 8 or more (or 12 or more) 26 or less, 8 or more (or 12 or more) 22 or less, 10 or more and 30 or less (or 26 or less). ), Or it may be 10 or more and 22 or less.
  • the polymer compound having a hydrophilic group and a hydrophobic group corresponds to a nonionic surfactant.
  • the repeating structure of the oxyethylene unit exhibits high hydrophilicity and can be a hydrophilic group in nonionic surfactants. Therefore, it is preferable that the polymer compound having a hydrophobic group described above contains a repeating structure of an oxyethylene unit. Due to the balance between hydrophobicity and high hydrophilicity due to the repeating structure of the oxyethylene unit, such a polymer compound can suppress excessive coverage of the surface of lead while selectively adsorbing to lead. It is possible to further reduce ear thinning while reducing liquid loss. Such a polymer compound can ensure high adsorptivity to lead even if it has a relatively low molecular weight (for example, Mn is 1000 or less).
  • polyoxypropylene-polyoxyethylene block copolymers etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units, and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • etherified compounds of hydroxy compounds having a repeating structure of oxyethylene units and esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • esterified compounds of hydroxy compounds having a repeating structure of oxyethylene units are nonions.
  • a surfactant corresponds to a surfactant.
  • the repeating structure of the oxyethylene unit corresponds to a hydrophilic group
  • the repeating structure of the oxypropylene unit corresponds to a hydrophobic group.
  • Such copolymers are also included in the polymer compound having a hydrophobic group.
  • Examples of the polymer compound having a hydrophobic group and containing a repeating structure of an oxyethylene unit include an etherified product of polyethylene glycol (alkyl ether and the like), an esterified product of polyethylene glycol (carboxylic acid ester and the like), and a polyethylene oxide adduct of the above-mentioned polyol.
  • Examples thereof include ethers (alkyl ethers and the like) of the above, and esterified products (carboxylic acid esters and the like) of polyethylene oxide adducts of the above-mentioned polyols (polyols and higher polyols and the like).
  • polymer compounds include polyethylene glycol oleate, polyethylene glycol dioleate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene coconut oil fatty acid sorbitan, polyoxyethylene sorbitan oleate, and polyoxystearate.
  • examples thereof include ethylene sorbitan, polyoxyethylene lauryl ether, polyoxyethylene tetradecyl ether, and polyoxyethylene cetyl ether.
  • the polymer compound is not limited to these.
  • an esterified product of polyethylene glycol an esterified product of the polyethylene oxide adduct of the above-mentioned polyol, or the like because it is possible to further reduce ear thinning and significantly reduce liquid reduction.
  • the repeating structure of the oxyC 2-4 alkylene may include at least the repeating structure of the oxypropylene unit.
  • Polymer compounds containing oxypropylene units have peaks from -CH ⁇ and -CH 2- of the oxypropylene units in the range of 3.2 ppm to 3.8 ppm in a chemical shift of 1 H-NMR spectrum. Since the electron densities around the nuclei of hydrogen atoms in these groups are different, the peaks are split.
  • Such a polymer compound has peaks in the chemical shift of 1 H-NMR spectrum, for example, in the range of 3.2 ppm or more and 3.42 ppm or less, and in the range of 3.42 ppm or more and 3.8 ppm or less. Peaks in the range of 3.2 ppm or more and 3.42 ppm or less are derived from -CH 2- , and peaks in the range of more than 3.42 ppm and 3.8 ppm or less are derived from -CH ⁇ and -CH 2- .
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, a copolymer containing the repeating structure of the oxypropylene unit, a polypropylene oxide adduct of the above-mentioned polyol, an etherified product or an esterified product thereof.
  • Examples of the copolymer include an oxypropylene-oxyalkylene copolymer (however, the oxyalkylene is C 2-4 alkylene other than oxypropylene).
  • Examples of the oxypropylene-oxyalkylene copolymer include an oxypropylene-oxyethylene copolymer and an oxypropylene-oxytrimethylene copolymer.
  • the oxypropylene-oxyalkylene copolymer may be referred to as a polyoxypropylene-polyoxyalkylene copolymer (for example, a polyoxypropylene-polyoxyethylene copolymer).
  • the oxypropylene-oxyalkylene copolymer may be a block copolymer (for example, a polyoxypropylene-polyoxyethylene block copolymer).
  • Examples of the etherified product include polypropylene glycol alkyl ether, alkyl ether of an oxypropylene-oxyalkylene copolymer (alkyl ether of a polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • esterified product examples include polypropylene glycol ester of carboxylic acid, carboxylic acid ester of oxypropylene-oxyalkylene copolymer (carboxylic acid ester of polyoxypropylene-polyoxyethylene copolymer, etc.) and the like.
  • Examples of the polymer compound containing at least the repeating structure of the oxypropylene unit include polypropylene glycol, polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer and the like), polypropylene glycol alkyl ether (above). Alkyl ether (methyl ether, ethyl ether, butyl ether, etc.), which is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less carbon atoms) in which R2 may have a substituent, etc.), polyoxyethylene-polyoxypropylene.
  • Alkyl ether (alkyl ether (butyl ether, hydroxyhexyl ether, etc.) which is an alkyl having 10 or less (or 8 or less or 6 or less) carbon atoms in which R 2 may have a substituent), polypropylene glycol carboxylate ( Polypropylene glycol carboxylate (polypropylene glycol acetate, etc.) in which R 3 is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less), polypropylene oxide adduct of a polyol of triol or more (polypropylene oxide adduct of glycerin, etc.) ).
  • the polymer compound is not limited to these.
  • the proportion of the oxypropylene unit is, for example, 5 mol% or more, and may be 10 mol% or more or 20 mol% or more.
  • the proportion of the oxypropylene unit is, for example, 100 mol% or less.
  • the proportion of the oxypropylene unit may be 90 mol% or less, 75 mol% or less, 60 mol% or less, 50 mol% or less, or 43 mol% or less.
  • the proportion of the oxypropylene unit is 5 mol% or more and 100 mol% or less (or 90 mol% or less), 10 mol% or more and 100 mol% or less (or 90 mol% or less), 20 mol% or more and 100 mol%.
  • the proportion of the oxypropylene unit is 5 mol% or more and 100 mol% or less (or 90 mol% or less), 10 mol% or more and 100 mol% or less (or 90 mol% or less), 20 mol% or more and 100 mol%.
  • the polymer compound preferably contains a large amount of oxyC 2-4 alkylene unit from the viewpoint of increasing the adsorptivity of the polymer compound to lead and facilitating the formation of a linear structure of the polymer compound.
  • Such polymer compounds include, for example, an oxygen atom attached to a terminal group and an -CH 2 -group and / or -CH ⁇ group attached to an oxygen atom.
  • the ratio of the peak of hydrogen atom to the integrated value of the peak becomes large.
  • This ratio is, for example, 50% or more, and may be 80% or more. From the viewpoint that the effect of reducing the ear thinning of the negative electrode plate is further enhanced and the effect of reducing the liquid reduction is further enhanced, the above ratio is preferably 85% or more, more preferably 90% or more.
  • the polymer compound has a -OH group at the end and has -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom of this -OH group, 1 in the H-NMR spectrum, -CH 2
  • the peaks of the hydrogen atoms of the -group and -CH ⁇ group are in the range of chemical shifts of more than 3.8 ppm and less than 4.0 ppm.
  • the negative electrode material may contain one kind of polymer compound or two or more kinds.
  • the polymer compound may contain a compound having Mn of 300 or more or 400 or more, a compound having Mn of 500 or more, a compound having Mn of 600 or more, and a compound having Mn of 1000 or more.
  • the Mn of such a compound is, for example, 5 million or less, may be 1 million or less or 100,000 or less, may be 50,000 or less or 20,000 or less, and may be 15,000 or less or 10,000 or less. ..
  • the Mn of the compound is preferably 5000 or less, and may be 4000 or less or 3000 or less.
  • the polymer compound two or more kinds of compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the molecular weight distribution.
  • the Mn of the above compounds is 3 or more and 5 million or less (or 1 million or less), 4 or more and 5 million or less (or 1 million or less), 5 or more and 5 million or less (or 1 million or less), and 6 or more and 5 million or less (or).
  • the polymer compound preferably contains a compound having at least Mn of 1000 or more.
  • the Mn of such a compound may be 1000 or more and 50,000 or less, 1000 or more and 20000 or less, 1000 or more and 15000 or less, or 1000 or more and 10000 or less.
  • the Mn of the compound is preferably 1000 or more and 5000 or less, may be 1000 or more and 4000 or less, and is 1000 or more and 3000 or less. You may.
  • the effect of reducing the liquid reduction can be further enhanced.
  • the compound having Mn as described above easily moves into the negative electrode material even when it is contained in the electrolytic solution, the compound can be replenished in the negative electrode material, and the negative electrode material can be replenished from this viewpoint as well. It is easy to hold the compound inside.
  • the polymer compound two or more kinds of compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the molecular weight distribution.
  • the content of the polymer compound in the negative electrode electrode material is, for example, 8 ppm or more and may be 10 ppm or more on a mass basis. From the viewpoint of further improving the effect of reducing ear thinning, the content of the polymer compound in the negative electrode electrode material is preferably 15 ppm or more on a mass basis. When the content of the polymer compound is in such a range, the hydrogen generation voltage can be more easily increased, and the effect of suppressing the liquid reduction can be further enhanced.
  • the content (mass basis) of the polymer compound in the negative electrode electrode material is, for example, 400 ppm or less, and may be 380 ppm or less or 370 ppm or less.
  • the content (mass basis) of the polymer compound is 8 ppm or more (or 10 ppm or more) 400 ppm or less, 8 ppm or more (or 10 ppm or more) 380 ppm or less, 8 ppm or more (or 10 ppm or more) 370 ppm or less, 15 ppm or more and 400 ppm or less (or 380 ppm or less). Alternatively, it may be 15 ppm or more and 370 ppm or less.
  • the negative electrode material may contain an organic shrinkage proofing agent.
  • an organic shrinkage proofing agent at least one selected from the group consisting of a lignin compound and a synthetic organic shrinkage proofing agent may be used.
  • the lignin compound include lignin and lignin derivatives.
  • the lignin derivative include lignin sulfonic acid or a salt thereof (alkali metal salt (sodium salt, etc.), etc.).
  • Organic shrinkage proofing agents are usually roughly classified into lignin compounds and synthetic organic shrinkage proofing agents. It can be said that the synthetic organic shrinkage proofing agent is an organic shrinkage proofing agent other than the lignin compound.
  • the synthetic organic shrinkage proofing agent is an organic polymer containing a sulfur element, and generally contains a plurality of aromatic rings in the molecule and also contains a sulfur element as a sulfur-containing group.
  • a sulfur element as a sulfur-containing group.
  • the sulfur-containing groups a sulfonic acid group or a sulfonyl group, which is a stable form, is preferable.
  • the sulfonic acid group may be present in acid form or may be present in salt form such as Na salt.
  • the negative electrode electrode material may contain one kind of organic shrinkage proofing agent, or may contain two or more kinds of organic shrinkage proofing agents.
  • the organic shrinkage proofing agent it is preferable to use a condensate containing at least a unit of an aromatic compound.
  • a condensate include a condensate of an aromatic compound made of an aldehyde compound (such as at least one selected from the group consisting of aldehydes (eg, formaldehyde) and condensates thereof).
  • the organic shrinkage proofing agent may contain a unit of one kind of aromatic compound, or may contain a unit of two or more kinds of aromatic compounds.
  • the unit of the aromatic compound means a unit derived from the aromatic compound incorporated in the condensate.
  • Examples of the aromatic ring contained in the aromatic compound include a benzene ring and a naphthalene ring.
  • the plurality of aromatic rings may be directly bonded or linked by a linking group (for example, an alkylene group (including an alkylidene group), a sulfone group) or the like.
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include compounds having the above aromatic ring and at least one selected from the group consisting of a hydroxy group and an amino group.
  • the hydroxy group or amino group may be directly bonded to the aromatic ring, or may be bonded as an alkyl chain having a hydroxy group or an amino group.
  • the hydroxy group also includes a salt of the hydroxy group (-OMe).
  • the amino group also includes a salt of the amino group (specifically, a salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.), Group 2 metals of the periodic table (Ca, Mg, etc.) and the like.
  • the aromatic compound examples include bisarene compounds [bisphenol compounds, hydroxybiphenyl compounds, bisarene compounds having an amino group (bisarylalkane compounds having an amino group, bisarylsulfone compounds having an amino group, biphenyl compounds having an amino group, etc.), and the like. Hydroxyarene compounds (hydroxynaphthalene compounds, phenol compounds, etc.), aminoarene compounds (aminonaphthalene compounds, aniline compounds (aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid, etc.), etc.), etc.] are preferable.
  • the aromatic compound may further have a substituent.
  • the organic shrinkage proofing agent may contain one kind of residues of these compounds, or may contain a plurality of kinds.
  • bisphenol compound bisphenol A, bisphenol S, bisphenol F and the like are preferable.
  • the condensate preferably contains at least a unit of an aromatic compound having a sulfur-containing group.
  • a condensate containing at least a unit of a bisphenol compound having a sulfur-containing group is used, the effect of suppressing ear thinning can be further enhanced.
  • the sulfur-containing group may be directly bonded to the aromatic ring contained in the compound, or may be bonded to the aromatic ring as an alkyl chain having a sulfur-containing group, for example.
  • the sulfur-containing group is not particularly limited, and examples thereof include a sulfonyl group, a sulfonic acid group, or a salt thereof.
  • the organic shrinkage proofing agent for example, a condensation containing at least one selected from the group consisting of a unit of the above-mentioned bisarene compound and a unit of a monocyclic aromatic compound (hydroxyarene compound and / or aminoarene compound, etc.). At least one may be used.
  • the organic shrinkage proofing agent may contain at least a condensate containing a unit of a bisarene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bis-alene compound and a monocyclic aromatic compound made of an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (such as phenol sulfonic acid or a substitute thereof) is preferable.
  • aminoarene compound aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid and the like are preferable.
  • monocyclic aromatic compound a hydroxyarene compound is preferable.
  • the content of the organic shrinkage proofing agent contained in the negative electrode electrode material is, for example, 0.01% by mass or more, and may be 0.05% by mass or more.
  • the content of the organic shrinkage proofing agent is, for example, 1.0% by mass or less, and may be 0.5% by mass or less.
  • the content of the organic shrinkage-proofing agent contained in the negative electrode electrode material is 0.01% by mass or more and 1.0% by mass or less, 0.05% by mass or more and 1.0% by mass or less, and 0.01% by mass or more and 0.5. It may be mass% or less, or 0.05 mass% or more and 0.5 mass% or less.
  • Carbonate material As the carbonaceous material contained in the negative electrode electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, furnace black, and lamp black. Furness Black also includes Ketjen Black (trade name).
  • the graphite may be any carbonaceous material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite.
  • the negative electrode material may contain one kind of carbonaceous material, or may contain two or more kinds.
  • the content of the carbonaceous material in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more.
  • the content of the carbonaceous material is, for example, 5% by mass or less, and may be 3% by mass or less.
  • the content of the carbonaceous material in the negative electrode material is 0.05% by mass or more and 5% by mass or less, 0.05% by mass or more and 3% by mass or less, 0.10% by mass or more and 5% by mass or less, or 0.10. It may be mass% or more and 3 mass% or less.
  • barium sulfate The content of barium sulfate in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more. The content of barium sulfate in the negative electrode electrode material is, for example, 3% by mass or less, and may be 2% by mass or less.
  • the content of barium sulfate in the negative electrode material is 0.05% by mass or more and 3% by mass or less, 0.05% by mass or more and 2% by mass or less, 0.10% by mass or more and 3% by mass or less, or 0.10% by mass. It may be% or more and 2% by mass or less.
  • Chloroform-soluble components are recovered from the chloroform solution in which the polymer compound obtained by extraction is dissolved by distilling off chloroform under reduced pressure.
  • the chloroform-soluble component is dissolved in deuterated chloroform, and the 1 H-NMR spectrum is measured under the following conditions. From this 1 H-NMR spectrum, a peak with a chemical shift in the range of 3.2 ppm or more and 3.8 ppm or less is confirmed. Further, the type of oxyC 2-4 alkylene unit is specified from the peak in this range.
  • V 1 From the 1 H-NMR spectrum, the integral value (V 1 ) of the peaks in which the chemical shift exists in the range of 3.2 ppm or more and 3.8 ppm or less is obtained.
  • V 2 the sum of the integrated values of the peaks in the 1 H-NMR spectrum
  • the integral value of the peak in the 1 H-NMR spectrum when the integral value of the peak in the 1 H-NMR spectrum is obtained, two points in the 1 H-NMR spectrum having no significant signal so as to sandwich the corresponding peak are determined, and these two points are determined.
  • Each integrated value is calculated using the straight line connecting the intervals as the baseline. For example, for a peak in which the chemical shift is in the range of 3.2 ppm to 3.8 ppm, the straight line connecting the two points of 3.2 ppm and 3.8 ppm in the spectrum is used as the baseline. For example, for a peak in which the chemical shift exceeds 3.8 ppm and exists in the range of 4.0 ppm or less, the straight line connecting the two points of 3.8 ppm and 4.0 ppm in the spectrum is used as the baseline.
  • Na and Ma averaged the Na and Ma values of each monomer unit using the molar ratio (mol%) of each monomer unit contained in the repeating structure, respectively. The value.
  • the integrated value of the peak in the 1 H-NMR spectrum is obtained by using the data processing software "ALICE” manufactured by JEOL Ltd.
  • the infrared spectroscopic spectrum measured using the sample B of the organic shrinkage proofing agent thus obtained the ultraviolet visible absorption spectrum measured by diluting the sample B with distilled water or the like and measuring with an ultraviolet visible absorptiometer, and the sample B being used as heavy water or the like.
  • the structural formula of the organic shrinkage proofing agent cannot be specified exactly, so that the same organic shrinkage proofing is applied to the calibration curve.
  • the agent may not be available.
  • calibration is performed using an organic shrink-proof agent extracted from the negative electrode of the battery and a separately available organic polymer having a similar shape in the ultraviolet-visible absorption spectrum, the infrared spectroscopic spectrum, the NMR spectrum, and the like. By creating a line, the content of the organic shrink-proofing agent is measured using the ultraviolet-visible absorption spectrum.
  • a carbonaceous material and components other than barium sulfate are removed from the dispersion liquid using a sieve.
  • the dispersion liquid is suction-filtered using a membrane filter whose mass has been measured in advance, and the membrane filter is dried together with the filtered sample in a dryer at 110 ° C. ⁇ 5 ° C.
  • the filtered sample is a mixed sample of a carbonaceous material and barium sulfate.
  • the mass of the sample C (M m ) is measured by subtracting the mass of the membrane filter from the total mass of the dried mixed sample (hereinafter referred to as sample C) and the membrane filter.
  • the sample C is put into a crucible together with a membrane filter and incinerated at 1300 ° C. or higher.
  • the remaining residue is barium oxide.
  • the mass of barium oxide is converted into the mass of barium sulfate to obtain the mass of barium sulfate ( MB ).
  • the mass of the carbonaceous material is calculated by subtracting the mass MB from the mass M m .
  • the negative electrode plate can be formed by applying or filling a negative electrode paste to a negative electrode current collector, aging and drying to produce an unchemical negative electrode plate, and then forming an unchemical negative electrode plate.
  • the negative electrode paste is, for example, a lead powder, a polymer compound, and, if necessary, at least one selected from the group consisting of an organic shrinkage proofing agent, a carbonaceous material, and other additives, and water and sulfuric acid (or an aqueous solution of sulfuric acid). ) Is added and kneaded to produce. At the time of aging, it is preferable to ripen the unchemical negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group. The formation produces spongy lead.
  • the positive electrode plate of a lead storage battery can be classified into a paste type, a clad type and the like. Either a paste type or a clad type positive electrode plate may be used.
  • the paste type positive electrode plate includes a positive electrode current collector and a positive electrode material. The positive electrode material is held in the positive current collector. In the paste-type positive electrode plate, the positive electrode material is a portion of the positive electrode plate excluding the positive electrode current collector.
  • the positive electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing.
  • a grid-shaped current collector As the positive electrode current collector because it is easy to support the positive electrode material.
  • a plurality of porous tubes, a core metal (spine) inserted in each tube, a current collector connecting the plurality of core metal (spine), and a core metal (spine) are inserted. It is provided with a positive electrode material filled in the formed tube and a spine projector connecting a plurality of tubes.
  • the positive electrode material is a portion of the positive electrode plate excluding the tube, the core metal (spine), the current collector, and the spine projector.
  • the core metal (spine) and the current collector may be collectively referred to as a positive electrode current collector.
  • the positive electrode plate may be attached to the positive electrode plate. Since such a member (pasting member) is used integrally with the positive electrode plate, it is included in the positive electrode plate.
  • the positive electrode plate includes a sticking member (mat, pacing paper, etc.)
  • the positive electrode electrode material is a portion of the positive electrode plate excluding the positive electrode current collector and the sticking member from the positive electrode plate.
  • the positive electrode current collector may include a surface layer.
  • the composition of the surface layer and the inner layer of the positive electrode current collector may be different.
  • the surface layer may be formed on a part of the positive electrode current collector.
  • the surface layer may be formed only on the lattice portion, the ear portion, or the frame bone portion of the positive electrode current collector.
  • the positive electrode material contained in the positive electrode plate contains a positive electrode active material (lead dioxide or lead sulfate) that develops a capacity by a redox reaction.
  • the positive electrode material may contain other additives, if necessary.
  • the unchemical paste type positive electrode plate is obtained by filling a positive electrode current collector with a positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by kneading lead powder, additives, water, and sulfuric acid.
  • lead powder or slurry-like lead powder is filled in a porous tube into which a core metal (spine) connected by a current collector is inserted, and a plurality of tubes are connected to each other (spine projector). ) Is formed. Then, a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical formation may be performed before assembling the lead-acid battery or the electrode plate group.
  • a separator can be arranged between the negative electrode plate and the positive electrode plate.
  • As the separator at least one selected from a non-woven fabric and a microporous membrane is used.
  • Nonwoven fabric is a mat that is entwined without weaving fibers, and is mainly composed of fibers.
  • the non-woven fabric for example, 60% by mass or more of the non-woven fabric is formed of fibers.
  • the fiber glass fiber, polymer fiber (polyolefin fiber, acrylic fiber, polyester fiber (polyethylene terephthalate fiber, etc.), etc.), pulp fiber, and the like can be used. Of these, glass fiber is preferable.
  • the nonwoven fabric may contain components other than fibers (for example, acid-resistant inorganic powder, polymer as a binder) and the like.
  • the microporous film is a porous sheet mainly composed of components other than fiber components.
  • a composition containing a pore-forming agent is extruded into a sheet and then the pore-forming agent is removed to form pores. It is obtained by.
  • the microporous membrane is preferably composed of a material having acid resistance, and a microporous membrane mainly composed of a polymer component is preferable.
  • the polymer component polyolefin (polyethylene, polypropylene, etc.) is preferable.
  • the pore-forming agent include at least one selected from the group consisting of polymer powders and oils.
  • the separator may be composed of, for example, only a non-woven fabric or only a microporous membrane. Further, the separator may be a laminate of a non-woven fabric and a microporous film, a material obtained by laminating different or similar materials, or a material in which irregularities are engaged with different or similar materials, as required.
  • the separator may be in the shape of a sheet or in the shape of a bag.
  • a sheet-shaped separator may be sandwiched between the positive electrode plate and the negative electrode plate.
  • the electrode plate may be arranged so as to sandwich the electrode plate with one sheet-shaped separator in a bent state.
  • the positive electrode plate sandwiched between the bent sheet-shaped separators and the negative electrode plate sandwiched between the bent sheet-shaped separators may be overlapped, and one of the positive electrode plate and the negative electrode plate may be sandwiched between the bent sheet-shaped separators. , May be overlapped with the other electrode plate.
  • the sheet-shaped separator may be bent in a bellows shape, and the positive electrode plate and the negative electrode plate may be sandwiched between the bellows-shaped separators so that the separator is interposed between them.
  • the separator may be arranged so that the bent portion is along the horizontal direction of the lead storage battery (for example, the bent portion is parallel to the horizontal direction), or along the vertical direction. (For example, the separator may be arranged so that the bent portion is parallel to the vertical direction).
  • recesses are alternately formed on both main surface sides of the separator.
  • the positive electrode plate is formed only in the concave portion on one main surface side of the separator.
  • a negative electrode plate is arranged (that is, a double separator is interposed between the adjacent positive electrode plate and the negative electrode plate).
  • the separator is arranged so that the bent portion is along the vertical direction of the lead storage battery, the positive electrode plate can be accommodated in the recess on one main surface side and the negative electrode plate can be accommodated in the recess on the other main surface side (that is,).
  • the separator can be in a single interposition between the adjacent positive electrode plate and the negative electrode plate).
  • the bag-shaped separator may accommodate a positive electrode plate or a negative electrode plate.
  • the maximum thickness T of the separator is, for example, 0.7 mm or more.
  • the maximum thickness T of the separator is, for example, 0.95 mm or less.
  • the maximum thickness T of the separator is measured for a sample obtained by removing sulfuric acid from a separator taken out from a fully charged lead-acid battery by washing with water and drying under atmospheric pressure. More specifically, a cross-sectional photograph of each separator sample in the thickness direction is taken, and the maximum thickness t is measured in this cross-sectional photograph.
  • the maximum thickness T can be obtained by averaging the maximum thickness t of all the separators included in the electrode plate group in the electrode plate group. In a lead-acid battery including a plurality of plates connected in series, the maximum thickness T of the separator is one plate group (cell) located at the end and one plate group (cell) located near the center. ) Is the average value.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the electrolytic solution may contain the above-mentioned polymer compound.
  • the electrolytic solution may contain a cation (for example, a metal cation) and / or an anion (for example, an anion other than the sulfate anion (for example, a phosphate ion)), if necessary.
  • a cation for example, a metal cation
  • an anion for example, an anion other than the sulfate anion (for example, a phosphate ion)
  • the metal cation include at least one selected from the group consisting of Na ion, Li ion, Mg ion, and Al ion.
  • the specific gravity of the electrolytic solution in a fully charged lead storage battery at 20 ° C. is, for example, 1.20 or more, and may be 1.25 or more.
  • the specific gravity of the electrolytic solution at 20 ° C. is 1.35 or less, preferably 1.32 or less.
  • the specific gravity of the electrolytic solution at 20 ° C. may be 1.20 or more and 1.35 or less, 1.20 or more and 1.32 or less, 1.25 or more and 1.35 or less, or 1.25 or more and 1.32 or less. ..
  • the lead-acid battery can be obtained by a manufacturing method including a step of accommodating a group of plates and an electrolytic solution in a cell chamber of an electric tank.
  • Each cell of the lead-acid battery includes a group of plates and an electrolytic solution housed in each cell chamber.
  • the electrode plate group is assembled by laminating the positive electrode plate, the negative electrode plate, and the separator so that the separator is interposed between the positive electrode plate and the negative electrode plate prior to the accommodation in the cell chamber.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared prior to assembling the electrode plate group.
  • the method for manufacturing a lead-acid battery may include, if necessary, a step of forming at least one of a positive electrode plate and a negative electrode plate after a step of accommodating a group of electrode plates and an electrolytic solution in a cell chamber.
  • Each electrode plate in the electrode plate group may be one plate or two or more plates.
  • the number of negative electrode plates included in the electrode plate group is preferably two or more, and may be four or more or six or more. Further, when the number of negative electrode plates included in the electrode plate group is 9 or more, the decrease in the specific gravity of the electrolytic solution in the upper part of the electrode plate group in the PSOC cycle is suppressed, and lead is difficult to dissolve in the selvage. The effect of reducing ear thinning is further enhanced.
  • the number of positive electrode plates included in the electrode plate group is n
  • the electrode distance D is obtained from the pitch between the pair of adjacent positive electrode plates and the thickness of each of the positive electrode plate and the negative electrode plate for the electrode plate group taken out from the fully charged lead storage battery.
  • the pitch is measured at the bottom of the cross section of the shelf that connects the selvages of the plurality of positive electrodes in parallel.
  • the electrode plate group includes 6 positive electrode plates and 7 negative electrode plates
  • the distance between the centers of the ears is measured at 5 points
  • the pitch is obtained by averaging.
  • the electrode plate group is composed of 7 positive electrode plates and 7 negative electrode plates
  • the distance between the centers of the ears is measured at 6 points, and the pitch is obtained by averaging.
  • the pitch is an average value obtained for any two electrode plate groups (cells). For example, in the case of a 12V lead-acid battery containing 6 electrode plates, the distance between the centers of the ears is measured and averaged in the electrode plates of the 1st cell and the 4th cell counting from the positive electrode terminal side. Pitch is required.
  • each electrode plate is measured, for example, along the peripheral edge of the electrode plate at three points (total of eight points: positions indicated by numbers 1 to 8 in FIG. 6) near both ends and the center per side with a micrometer. , Average.
  • the positive electrode plate is washed with water to remove sulfuric acid and dried under atmospheric pressure before measuring the thickness
  • the negative electrode plate is washed with water to remove sulfuric acid and vacuum dried (dried under pressure lower than atmospheric pressure). Measure the thickness.
  • the thickness of the electrode plate shall be the thickness including the mat. This is because the mat is used integrally with the electrode plate. However, when the mat is attached to the separator, the thickness of the mat is included in the thickness of the separator.
  • DT is in such a range, the decrease in the specific gravity of the electrolytic solution in the upper part of the electrode plate group in the PSOC cycle is suppressed, so that lead is hard to dissolve in the ear, and thus the effect of reducing ear thinning is achieved. Will increase further.
  • DT is, for example, ⁇ 1.5 mm or more.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 for accommodating a plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of refilling water, the liquid spout 18 is removed and the refilling liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is configured by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 via a separator 4, respectively.
  • the bag-shaped separator 4 accommodating the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connection body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel is connected.
  • 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf portion 6, and the penetration connecting body 8 is connected to the positive electrode shelf portion 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf 5 is formed by welding the ears provided on the upper part of each positive electrode plate 3 by a cast-on-strap method or a burning method.
  • the negative electrode shelf portion 6 is also formed by welding the selvage portions provided on the upper portions of the negative electrode plates 2 as in the case of the positive electrode shelf portion 5.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure may be provided with a reflux structure between the inner lid and the outer lid for returning the electrolytic solution to the inside of the battery (inside the inner lid) from the reflux port provided on the inner lid.
  • each of the ear thinning amount, the liquid reducing performance, and the PSOC life performance is evaluated by the following procedure.
  • the rated voltage of the test battery used for the evaluation is 12V, and the rated 5-hour rate capacity is 48Ah.
  • the negative electrode plate is taken out from the test battery, washed with water, dried, and the thickness of the ear portion (initial thickness: t 0 ) is measured.
  • the test battery is charged and discharged according to the PSOC charge / discharge pattern (specifically, the pattern shown in Table 1) of the battery industry association standard SBA S 0101 (lead-acid battery for idling stop vehicle).
  • the negative electrode plate is taken out from the lead-acid battery after charging and discharging, washed with water, and dried. Next, the negative electrode plate is impregnated with an epoxy resin and cured.
  • the metallurgical microscope GX53F manufactured by OLYMPUS is used. The thickness of the selvage is determined by measuring the thickness of any five points of the selvage with a caliper and averaging them.
  • (B) Evaluation 2 Liquid reduction performance Using a test battery, the amount of decrease in the electrolytic solution is determined from the mass change of the test battery before and after the high temperature durability test. More specifically, the mass (M 0 ) of the test battery is measured before the high temperature durability test. The test battery is subjected to a high temperature durability test by repeating the following discharge and charge cycles 5000 times in a water tank at 75 ° C. ⁇ 3 ° C. Measure the mass (M 1 ) of the test battery after the high temperature durability test. By subtracting M 1 from M 0 , the amount of decrease in the electrolytic solution is obtained. Discharge: 25A, 2 minutes Charge: 14.8V, 25A, 10 minutes
  • (D) Evaluation 4 Potential change in the selvage of the negative electrode plate Using a test battery, charging and discharging are performed under the same conditions as in the evaluation 3, and the change in the potential of the selvage of the negative electrode plate at this time is measured. The potential of the selvage portion of each negative electrode plate is measured using a lead reference electrode (Pb / PbSO 4 ).
  • the lead-acid batteries according to one aspect of the present invention are summarized below.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage has a surface layer containing Sn and The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material is a lead-acid battery containing a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum measured using deuterated chloroform as a solvent.
  • the polymer compound contains an oxygen atom bonded to a terminal group and an -CH 2 -group and / or -CH ⁇ group bonded to the oxygen atom.
  • the integral value of the peak, the integral value of the peak of the -CH2 -group hydrogen atom, and the integral value of the peak of the -CH ⁇ group hydrogen atom account for the sum of the peak.
  • the ratio of the integrated values may be 85% or more.
  • the polymer compound may contain a repeating structure of an oxyC 2-4 alkylene unit.
  • the lead-acid battery comprises at least one cell comprising a group of plates and an electrolyte.
  • the electrode plate group includes a negative electrode plate, a positive electrode plate, and a separator interposed between the negative electrode plate and the positive electrode plate.
  • the negative electrode plate includes a current collector provided with an ear portion and a negative electrode electrode material.
  • the selvage has a surface layer containing Sn and The Sn content in the surface layer is less than 10% by mass.
  • the negative electrode material is a lead storage battery containing a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit.
  • the Sn content in the surface layer may be 7% by mass or less, 6% by mass or less, or 5% by mass or less.
  • the Sn content in the surface layer is 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more. You may.
  • the thickness of the surface layer may be 0.01 mm or more, 0.015 mm or more, or 0.02 mm or more.
  • the thickness of the surface layer may be 0.1 mm or less or 0.05 mm or less.
  • the polymer compound may contain a compound having Mn of 300 or more, 400 or more, 500 or more, 600 or more, or 1000 or more.
  • the polymer compound has Mn of 5 million or less, 1 million or less, 100,000 or less, 50,000 or less, 20000 or less, 15000 or less, 10000 or less, 5000 or less. It may contain 4000 or less or 3000 or less compounds.
  • the polymer compound is a hydroxy compound having a repeating structure of an oxyC 2-4 alkylene unit, an etherified product of the hydroxy compound, and an ester of the hydroxy compound. Containing at least one selected from the group consisting of compounds
  • the hydroxy compound is at least one selected from the group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a poly C 2-4 alkylene oxide adduct of a polyol. There may be.
  • the polymer compound may contain at least a repeating structure of an oxypropylene unit.
  • the polymer compound is polypropylene glycol, a polyoxypropylene-polyoxyethylene copolymer (polyoxypropylene-polyoxyethylene block copolymer, etc.), or a polypropylene glycol alkyl ether (the above R 2 ).
  • a polyoxypropylene-polyoxyethylene copolymer polyoxypropylene-polyoxyethylene block copolymer, etc.
  • a polypropylene glycol alkyl ether the above R 2 .
  • polypropylene glycol carboxylate (Or 8 or less or 6 or less) alkyl ethers (butyl ether, hydroxyhexyl ether, etc.), polypropylene glycol carboxylate (R 3 above is an alkyl having 10 or less carbon atoms (or 8 or less or 6 or less)). It may contain at least one selected from the group consisting of polypropylene glycol carboxylate (such as polypropylene glycol acetate) and polypropylene oxide adducts of triol or higher polyols (such as polypropylene oxide adducts of glycerin).
  • polypropylene glycol carboxylate such as polypropylene glycol acetate
  • polypropylene oxide adducts of triol or higher polyols such as polypropylene oxide adducts of glycerin.
  • the proportion of the oxypropylene unit in the polymer compound may be 5 mol% or more, 10 mol% or more, or 20 mol% or more.
  • the proportion of the oxypropylene unit in the polymer compound is 100 mol% or less, 90 mol% or less, 75 mol% or less, 60 mol% or less, 50 mol% or less, Alternatively, it may be 43 mol% or less.
  • the content of the polymer compound in the negative electrode electrode material may be 8 ppm or more, 10 ppm or more, or 15 ppm or more on a mass basis. ..
  • the content of the polymer compound in the negative electrode electrode material may be 400 ppm or less, 380 ppm or less, or 370 ppm or less on a mass basis. ..
  • the negative electrode electrode material may further contain an organic shrinkage proofing agent.
  • the content of the organic shrinkage barrier in the negative electrode electrode material may be 0.01% by mass or more, or 0.05% by mass or more.
  • the content of the organic shrinkage barrier in the negative electrode electrode material may be 1.0% by mass or less, or 0.5% by mass or less.
  • the negative electrode electrode material may further contain a carbonaceous material.
  • the content of the carbonaceous material in the negative electrode electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the carbonaceous material in the negative electrode electrode material may be 5% by mass or less, or 3% by mass or less.
  • the negative electrode material may further contain barium sulfate.
  • the content of the barium sulfate in the negative electrode electrode material may be 0.05% by mass or more, or 0.10% by mass or more.
  • the content of the barium sulfate in the negative electrode electrode material may be 3% by mass or less, or 2% by mass or less.
  • the maximum thickness T of the separator may be 0.7 mm or more.
  • the maximum thickness T of the separator may be 0.95 mm or less.
  • the electrode plate group in at least one of the cells, includes two or more positive electrode plates and two or more negative electrode plates. Moreover, the positive electrode plate and the negative electrode plate are alternately laminated via the separator.
  • the electrode plate group may include nine or more negative electrode plates.
  • the number of negative electrode plates included in the electrode plate group is n
  • the electrolytic solution may contain Al ions.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.20 or more or 1.25 or more.
  • the specific gravity of the electrolytic solution in the fully charged lead-acid battery at 20 ° C. may be 1.35 or less or 1.32 or less.
  • a lattice having a surface layer thus formed in the selvage portion is used as a negative electrode current collector.
  • an expanded lattice made of a Pb—Ca—Sn-based alloy with no surface layer provided on the selvage is used.
  • Electrode paste Lead powder, water, dilute sulfuric acid, carbon black, polymer compound, sodium lignin sulfonate as an organic shrinkage proofing agent, and barium sulfate are mixed to obtain a negative electrode paste.
  • the contents of the organic shrinkage-proofing agent, carbon black, and barium sulfate in the negative electrode material obtained by the above-mentioned procedure are 0.1% by mass, 0.2% by mass, and 0.4, respectively.
  • the polymer compound the polymer compounds shown in Tables 2 to 4 are mixed together with each component so that the content of the polymer compound in the negative electrode electrode material obtained by the above-mentioned procedure becomes the value shown in Tables 2 to 4. .
  • the negative electrode paste is filled in the mesh portion of the negative electrode current collector and aged and dried to obtain an unchemicald negative electrode plate.
  • the unchemical negative electrode plate is housed in a bag-shaped separator formed of a polyethylene microporous film, and the electrode plate is composed of eight unchemical negative electrode plates and seven unchemical positive electrode plates. Form a group. A group of plates is inserted into an electric tank, a predetermined amount of sulfuric acid aqueous solution as an electrolytic solution is injected, and chemical formation is performed in the electric tank. The rated voltage of the lead battery is 12 V, and the rated capacity is 48 Ah (5). A liquid-type lead-acid battery with a time rate) is manufactured. The specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is 1.28. The lead-acid battery is fully charged due to the above chemical formation.
  • the oxyethylene unit is in the range of the chemical shift of 3.2 ppm or more and 3.8 ppm or less in the 1 H-NMR spectrum of the polymer compound measured by the above-mentioned procedure. A peak derived from -CH 2- is observed.
  • the 1 H-NMR spectrum of the polymer compound measured by the above procedure shows that the oxypropylene unit is in the range of a chemical shift of 3.2 ppm or more and 3.42 ppm or less.
  • Evaluation 1 Ear thinning amount The negative electrode plate is taken out from the lead storage battery produced above, and the ear thinning amount is determined by the procedure described above. The amount of ear thinning in each lead storage battery is evaluated by the relative ratio when the amount of ear thinning of the lead storage battery C1 is 1.
  • the results are shown in Tables 2 to 4.
  • the Mn of the polymer compound shown in Tables 2 to 4 is Mn obtained by the above-mentioned procedure.
  • E1 to E16 are examples, and C1 to C4 are comparative examples.
  • the negative electrode material does not contain a polymer compound and the Sn content in the surface layer of the selvage portion of the negative electrode plate is 10% by mass or 30% by mass, no surface layer is provided.
  • the amount of ear thinning can be greatly reduced from 10.5 to 1.2 or 1 (comparison between C4 and C2 and C1).
  • the Sn content in the surface layer is less than 10% by mass, the effect of reducing ear thinning is low (comparison between C4 and C3, comparison between C3 and C2 and C1).
  • the amount of ear thinning can be reduced when the negative electrode material contains a polymer compound (comparison between C3 and E1 to E3). Further, in E1 to E3, the amount of liquid reduction is also reduced.
  • the amount of ear thinning can be significantly reduced by containing the polymer compound in the negative electrode material (E4).
  • E4 the polymer compound in the negative electrode material
  • the ear thinning amount can be reduced by combining with the polymer compound. It is presumed that it can be reduced.
  • the Sn content in the surface layer may be less than 10% by mass, and even when it is 7% by mass or less or 5% by mass or less, the ear thinning can be remarkably reduced by the combination with the polymer compound.
  • the polymer content in the negative electrode material is preferably 15 ppm or more from the viewpoint of further enhancing the effect of reducing the amount of ear thinning.
  • the upper limit of the polymer content in the negative electrode electrode material is not particularly limited, but an excellent effect of reducing the amount of ear thinning can be obtained even at 400 ppm or less.
  • the unchemical negative electrode plate is housed in a bag-shaped separator formed of a polyethylene microporous film, and the unchemical negative electrode plate and the unchemical positive electrode plate are overlapped to form a group of electrode plates. Form.
  • the lead storage battery E17 seven unchemical negative electrode plates and six unchemical positive electrode plates are used.
  • the lead storage battery E18 eight unchemical negative electrode plates and seven unchemical positive electrode plates are used.
  • the lead storage battery E19 nine unchemical negative electrode plates and eight unchemical positive electrode plates are used.
  • As the electrolytic solution a sulfuric acid aqueous solution containing Al ions at a concentration of 17 g / L is used.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is 1.285. Except for these, lead-acid batteries E17 to E19 are manufactured in the same manner as in the case of lead-acid battery E1. E17 to E19 are examples.
  • the terminal voltage drops sharply when the PSOC cycle exceeds 50,000 or 60,000 times. Along with this sharp drop in the terminal voltage, the ear thinning of the negative electrode plate becomes remarkable, and the ear thinning leads to the end of its life.
  • the electrode plate group includes nine negative electrode plates, even if the PSOC cycle exceeds 100,000 times, no sharp decrease in the terminal voltage is observed, and the ear thinning of the negative electrode plates is suppressed.
  • the electrode plate group includes nine or more negative electrode plates.
  • Lead-acid batteries E20 to E23 and E24 to E27 By adjusting the sulfuric acid concentration, an electrolytic solution having a specific gravity of 1.20, 1.22, 1.24, 1.28 at 20 ° C. in a fully charged lead-acid battery is prepared.
  • Lead-acid batteries E20, E21, E22, and E23 are produced in the same manner as the lead-acid battery E19 except that the prepared electrolytic solution is used.
  • a sulfuric acid aqueous solution containing Na ions at a concentration of 7 g / L is used as the electrolytic solution.
  • an electrolytic solution having a fully charged lead-acid battery having a specific gravity of 1.20, 1.22, 1.24 or 1.28 at 20 ° C. is prepared.
  • Lead-acid batteries E24, E25, E26 and E27 are produced in the same manner as the lead-acid battery E19 except that the prepared electrolytic solution is used.
  • E20 to E23 and E24 to E27 are examples.
  • the amount of ear thinning of the negative electrode plate can be significantly reduced as compared with the case where Na ions are contained.
  • the lead-acid battery according to one aspect and the other aspect of the present invention is suitable for use in an idling stop start vehicle as, for example, a lead-acid battery for ISS that is charged and discharged under PSOC conditions.
  • the lead-acid battery can be suitably used, for example, as a power source for starting a vehicle (automobile, motorcycle, etc.) and an industrial power storage device (for example, a power source for an electric vehicle (forklift, etc.)). It should be noted that these are merely examples, and the use of the lead storage battery is not limited to these.
  • Negative electrode plate 3 Positive electrode plate 4: Separator 5: Positive electrode shelf part 6: Negative electrode shelf part 7: Positive electrode pillar 8: Through connection body 9: Negative electrode pillar 11: Electrode plate group 12: Electric tank 13: Bulk partition 14: Cell chamber 15: Lid 16: Negative electrode terminal 17: Positive electrode terminal 18: Liquid spout

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Abstract

L'invention concerne une batterie de stockage au plomb-acide comportant au moins un élément qui comporte un groupe de plaques d'électrode et une solution électrolytique. Le groupe de plaques d'électrode comprend une plaque d'électrode positive, une plaque d'électrode négative, et le séparateur qui est intercalé entre la plaque d'électrode positive et la plaque d'électrode négative. La plaque d'électrode négative comporte un collecteur qui a une partie de cosse, et un matériau d'électrode négative. La partie de cosse comporte une couche de surface qui contient du Sn. La teneur en Sn dans la couche de surface est inférieure à 10 % en masse. Le matériau d'électrode négative contient un composé polymère qui a un pic dans la plage de 3,2 ppm à 3,8 ppm dans le décalage chimique dans le spectre 1H–NMR tel que déterminé avec l'utilisation de chloroforme deutéré qui sert de solvant.
PCT/JP2021/039747 2020-11-27 2021-10-28 Batterie de stockage au plomb-acide WO2022113627A1 (fr)

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Citations (11)

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JPS5147237A (fr) * 1974-10-18 1976-04-22 Yuasa Battery Co Ltd
JPS60182662A (ja) * 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
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